CN103007784B - Improved preparation method of polypropylene hollow fiber separation membrane - Google Patents
Improved preparation method of polypropylene hollow fiber separation membrane Download PDFInfo
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Abstract
The invention relates to an improved preparation method of a polypropylene hollow fiber separation membrane. The invention belongs to the field of high-molecular material science. The method comprises the steps that: (1) polypropylene and a diluent are added into a kettle with a stirring device; heating and stirring are carried out, such that a membrane casting liquid is obtained; and when stirring is stopped, the liquid is subjected to standing and defoaming for 0.5-2h; (2) the membrane casting liquid is filtered by using a filter; an inner core liquid is introduced into a spinning nozzle, wherein a nozzle temperature is 145-165 DEG C; the inner core liquid and the membrane casting liquid are extruded by the spinning nozzle; the mixture first passes through air atmosphere, and then enters a multi-stage coagulating bath; the membrane casting liquid is cooled by the multi-stage coagulating bath, and the hollow fiber membrane is obtained by curing; (3) the hollow fiber membrane is wound by using a winding machine, and is extracted in one or a plurality of extraction agents; and (4) the extracted membrane is fetched and dried; and extraction agent is removed, such that the polypropylene hollow fiber separation membrane is obtained. With the method provided by the invention, under a same condition, a membrane flux is improved from 15/m<2>.h of one-stage water coagulating bath to higher than 1200/m<2>.h of two-stage coagulating bath.
Description
Technical field
The invention belongs to polymer material science field, relate to a kind of preparation method of polymeric membrane for separation, relate more specifically to the clotting method of the dual-bath coagulation of casting solution in a kind of polypropylene hollow fiber separation membrane preparation process.
Background technology
Polymeric membrane for separation is the macromolecule interfacial two kinds of homogeneous phase separating substances opened.Along with the development of membrane science technology, polymeric membrane for separation has been widely used in multiple industries such as water treatment, chemical industry, electronics, iron and steel, medical treatment, food.Polypropylene is as a kind of polyolefine material, premium properties such as being take propylene monomer as the main a kind of highly crystalline thermoplastic resin be polymerized, having that transparency is high, nontoxic, light specific gravity, easily processing, excellent in cushion effect, resistance to chemical attack, flex stiffiness, electrical insulating property are good.Because its function admirable, output are large, price is low, has great advantage as the membrane material tool preparing microporous barrier.
The method that the art prepares microporous polypropylene membrane mainly contains fusion drawn method and thermally induced phase separation (TIPS).Standby its shortcoming of microporous polypropylene membrane of fusion drawn legal system is that film strength is poor, and membrane aperture distribution is wide, membrane filtration low precision.And adopt thermally induced phase separation prepare microporous barrier by select suitable diluent, adjustment film-forming process and membrance casting condition carry out the controlled microporous barrier in obtained aperture.Thermally induced phase separation refer to by polymer and higher boiling, low volatility, low-molecular-weight solvent (generally higher than the fusing point of polymer) when high temperature, form homogeneous phase solution, then cooling down makes solution be separated, again solvent extraction is removed, the volume that solvent occupies becomes micropore, just becomes polymer microporous film.
The art adopts TIPS legal system to have many kinds for the technical method of microporous polypropylene membrane.Chinese patent CN101862601A discloses a kind of polypropylene hollow fiber microporous membrane and preparation method thereof, one or more combination in employing dibutyl phthalate, fatty amine, calcium stearate, isopropylamine alcohol, methylbenzene propyl ester, vegetable oil or diphenyl ether is as diluent, one or more combination in employing polyethylene glycol, methylphenol, polyvinylpyrrolidone, polyvinyl alcohol, isosorbite or double thioether is as additive, obtained casting solution, outer gel media film-forming is injected by spinning head together with inner gel medium.
Chinese patent CN1356410A discloses a kind of method that thermally induced phase separation prepares microporous polypropylene membrane, adopt vegetable oil, atoleine, diphenyl ether, machine oil as diluent, adipic acid, benzoic acid are as auxiliary agent, obtained homogeneous phase solution, polypropylene hollow fiber silk is spun into by spinning head, enter in water and solidify, then through extraction, obtained polypropylene hollow fiber separation membrane.
Chinese patent CN1718627A discloses a kind of microporous polypropylene membrane and preparation method thereof, by polypropylene and containing the diluent of vegetable oil according to constant weight proportioning, add thermal agitation, nature cooling curing obtains aggregate sample, then gets aggregate sample shave, puts into Flat bottom container, heating and melting is placed in water-bath and cools, add extractant extraction, put into vacuum drying oven drying evaporation, obtained microporous polypropylene membrane.
Chinese patent CN1597073A discloses a kind of method of preparing polypropylene plate micropore membrane using thermo phase separation, a certain proportion of PP GRANULES, diluent and auxiliary agent are heated, down on scraper plate after the obtained casting solution of stirring, in the certain thickness film of knifing indoor scraper scraping, scraper plate with film is put into running water to be extracted cold, then makes Polypropylene plates microporous barrier with extractant extraction.
Adopt TIPS legal system for microporous polypropylene membrane, its film-forming process, membrance casting condition etc. have remarkable impact to microcellular structural morphology.Scrape in membrane process in the spinning of hollow-fibre membrane and Flat Membrane, the coagulating bath that is cooled through of casting solution realizes, and coagulating bath serves and casting solution lowered the temperature and realizes the function that is separated film curing molding, is the external systems that film is separated.Existing TIPS legal system film adopts annular spinning jet spinning hollow-fibre membrane or employing to scrape film preparation Polypropylene plates microporous barrier, and using maximum is that the range of temperature of water is wide using nitrogen or water as the cooled and solidified medium of outer surface, and safety non-toxic, cost is low, and heat transfer is fast, and solidification rapidly.But for most of TIPS masking system, heat transfer water is fast, if only adopt one-level coagulating bath, and the component of coagulating bath be water or nitrogen time very easily obtain the uneven cortex of densification or aperture, and make microporous membrane permeation resistance higher, cause the lower through ability of film.
Summary of the invention
Technical problem solved by the invention: the preparation method that the invention provides a kind of polypropylene hollow fiber separation membrane of improvement, by selecting two-stage or multistage coagulating bath, and the component of coagulating bath at different levels, temperature and the time of staying are controlled, when adopting TIPS to prepare polypropylene hollow fiber separation membrane to solve in prior art, film outer surface cortex is fine and close, the problem of membrane pores skewness.
The technical solution used in the present invention:
The preparation method of the polypropylene hollow fiber separation membrane of a kind of improvement provided by the invention comprises following steps:
(1) in the still of agitating device, polypropylene and diluent is added, wherein polyacrylic mass fraction is 25 ~ 40%, polyacrylic melt index is 2.7 ~ 8g/10min, the mass fraction of diluent is 60 ~ 75%, be heated to 175 ~ 200 DEG C, stirring 0.5 ~ 3 hour under logical condition of nitrogen gas, obtaining casting solution through adding thermal agitation, stop stirring rear constant temperature standing and defoaming 0.5 ~ 2 hour;
(2) temperature is after the casting solution of 175 ~ 200 DEG C is filtered, and inner core liquid nitrogen gas is incorporated in spinning head, spinneret temperature is 140 ~ 175 DEG C, preferably 145 ~ 165 DEG C, extrude through spinning head together with the casting solution that temperature is 140 ~ 175 DEG C, at first through air atmosphere, then multistage coagulating bath is entered, be specially first through one-level coagulating bath, again through next stage coagulating bath, the component of every one-level coagulating bath in multistage coagulating bath, temperature, the time of staying control all separately, and casting solution is through multistage coagulating bath cooling down, and solidification obtains hollow-fibre membrane;
(3) hollow-fibre membrane is through up-coiler rolling, then puts into one or more extractants and extracts, extraction time 3 ~ 48h.；
(4) film extracted takes out drying, and drying means adopts drying means conventional in filming technology, obtains polypropylene hollow fiber separation membrane after removing extractant.
Described, polyacrylic mass fraction preferably 27 ~ 35%, polyacrylic melt index preferably 3 ~ 7g/10min in step (1), the mass fraction of diluent preferably 65 ~ 73%;
Described, diluent described in step (1) is mixture of a kind of or its combination in the middle of vegetable oil or phthalic acid ester, and at least containing a kind of phthalic acid ester in mixture, mass fraction is 10 ~ 90%.
Described phthalic acid ester is dibutyl phthalate or diamyl phthalate or phthalic acid two fat in heptan or o-phthalic acid dibutyl ester, is preferably dibutyl phthalate or o-phthalic acid dibutyl ester.
Described, in step (2), casting solution make use of air atmosphere after spinning head is extruded, and the effect of air is the volatilization place as diluent.Be advisable with 1 ~ 10cm in the air gap.
Described, in step (2), the kind of coagulating bath component should select the system close or compatible with diluent as far as possible.The kind of coagulating bath component can be one or more in water, polyalcohol, vegetable oil, phthalic acid ester, surfactant or glyceride.
Described vegetable oil is peanut oil or castor oil or soybean oil or corn oil, preferred soybean oil.
Described polyalcohol is ethanol, isopropyl alcohol, ethylene glycol, diglycol, triethylene-glycol, glycerine, polyethylene glycol.
Described surfactant is sodium sulfate of polyethenoxy ether of fatty alcohol, ethoxylated alkyl sulfate, neopelex.
The molecular weight of described polyethylene glycol is 200 ~ 600.
Described glyceride is glyceryl triacetate.
Described, in step (2), the control mode of coagulating bath adopts multistage coagulating bath, and wherein said multistage coagulating bath is at least two-stage coagulating bath; When adopting multistage coagulating bath, first through one-level coagulating bath, then through next stage coagulating bath; When adopting secondary coagulating bath, one-level coagulation bath temperature controls at 0 ~ 40 DEG C, preferably 0 ~ 20 DEG C, and secondary coagulation bath temperature controls at 0 ~ 80 DEG C, preferably 20 ~ 50 DEG C.One or more in one-level coagulating bath constituent species preferably vegetable oil, glyceryl triacetate, phthalic acid ester, glycerine, triethylene-glycol, low molecular polyethylene glycol, in secondary coagulating bath constituent species preferably vegetable oil, water, ethanol, surfactant, glycerine any one or multiple; The time of staying in one-level coagulating bath is 1 ~ 20s, and the time of staying in secondary coagulating bath is 1 ~ 20s, and the time of staying in coagulating bath at different levels is controlled by the stroke distances of adjustment in coagulating bath, and one-level coagulating bath is connected by guide wheel with secondary coagulating bath.
Described, in one-level coagulating bath, the mass fraction of selected component is 10 ~ 100%.In secondary coagulating bath, the mass fraction of selected component is 5 ~ 100%.
Described, step (3) described extractant is ketone or alcohol or alkane, and wherein ketone is preferably acetone, and alcohol is preferably methyl alcohol or ethanol or isopropyl alcohol, and alkane is preferably n-hexane or cyclohexane.
The essential distinction of the present invention and prior art is:
Patent of the present invention has carried out following improvement for the deficiencies in the prior art:
The present invention proposes a kind of preparation method of polypropylene hollow fiber separation membrane of improvement, by selecting the time of staying in the kind of coagulating bath component, concentration of component, coagulation bath temperature, coagulating bath progression and coagulating bath at different levels, and be applied to the preparation of polypropylene hollow fiber separation membrane, effectively control the structure of polypropylene hollow fiber separation membrane outer surface, avoid film outer surface and form fine and close cortex, the even aperture distribution of film, the polypropylene hollow fiber separation membrane outer surface micropore of preparation is controlled.
The invention has the beneficial effects as follows:
The present invention is selected by conditions such as the progression to coagulating bath, component, the time of staying and temperature, obtained polypropylene hollow fiber separation membrane is the diffusion barrier that outer surface cortex has controllable microhole structural, solve the problem of polypropylene hollow fiber separation membrane outer surface cortex densification, membrane flux significantly improves, one-level water condensation is bathed, when setting temperature is 20 DEG C, membrane flux is 15L/m
2h, and during two-stage coagulating bath, after the coagulating bath of one-level vegetable oil, enters the bath of secondary water condensation, and the temperature of secondary water condensation bath is all 20 DEG C and membrane flux brings up to 1200L/m
2more than h.The method is easy, is suitable for commercial introduction application, and therefore the inventive method goes for the outer surface structure control of polypropylene hollow fiber separation membrane.
Detailed description of the invention
Embodiment 1
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 25%, melt index is 2.7g/10min, take soya-bean oil as diluent, the mass fraction of diluent is 75%, is heated to 200 DEG C, and stirs 0.5 hour under logical condition of nitrogen gas, stop stirring rear constant temperature standing and defoaming 0.5 hour, obtain casting solution;
(2) casting solution (temperature 200 DEG C) filters through 100 order stainless steel filter screen, and adopt gear-type metering pump that casting solution is delivered to spinning head, be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 175 DEG C; Extrude doughnut, first through the air gap of 1cm, then enter 20 DEG C, mass fraction is stop 1s in the soya-bean oil of 100%, then in the water of 20 DEG C, stop 10s, after cooling curing, obtain polypropylene hollow fiber separation membrane.
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then hollow-fibre membrane is put into acetone, and extraction time is 3 hours;
(4) take out the film extracted, be placed in fume hood room temperature dry through air natural, after removing extractant, obtain polypropylene hollow fiber separation membrane of the present invention.Test its pure water flux and performance, adopt INSTRON 3343 Material Testing Machine to test its hot strength 3.6MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 65%, and average pore size is 0.22 μm.Testing its pure water flux under 0.1MPa is 1330L/m
2h.
Embodiment 2
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 40%, melt index is 8g/10min, with the mixture of soya-bean oil and o-phthalic acid dibutyl ester for diluent, in mixture, o-phthalic acid dibutyl ester mass fraction is 10%, and the mass fraction of diluent is 60%, be heated to 175 DEG C, and stir 3 hours under logical condition of nitrogen gas, stop stirring rear constant temperature standing and defoaming 2 hours, obtain casting solution;
(2) casting solution (temperature 175 DEG C) filters through 100 order stainless steel filter screen, and adopt gear-type metering pump that casting solution is delivered to spinning head, be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 140 DEG C; Extrude doughnut, first through the air gap of 2cm, then enter that temperature is 20 DEG C, mass fraction is stop 1s in the triethylene-glycol of 10%, then enter in 80 DEG C of aqueous solution and stop 10s, after cooling curing, obtain polypropylene hollow fiber separation membrane.
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then hollow-fibre membrane is put into methyl alcohol extracts, and extraction time is 48 hours;
(4) film extracted is taken out, be placed in fume hood room temperature dry through air natural, polypropylene hollow fiber separation membrane of the present invention is obtained after removing extractant, test its pure water flux and performance, INSTRON 3343 Material Testing Machine is adopted to test its hot strength 4.1MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 51%, and average pore size is 0.24 μm.Testing its pure water flux under 0.1MPa is 1285L/m
2h.
Embodiment 3
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, acrylic resin and diluent is added, polyacrylic mass fraction is 27%, melt index is 3g/10min, with the mixture of soya-bean oil and dibutyl phthalate (DBP) for diluent, in mixture, dibutyl phthalate (DBP) mass fraction is 90%, and the mass fraction of diluent is 73%, be heated to 180 DEG C, and stir 1 hour under logical condition of nitrogen gas, stop stirring rear constant temperature standing and defoaming 1 hour, obtain casting solution;
(2) casting solution (temperature 180 DEG C) filters through 100 order stainless steel filter screen, and adopt gear-type metering pump that casting solution is delivered to spinning head, be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 145 DEG C; Extrude doughnut, first through the air gap of 4cm, then enter 20 DEG C, mass fraction is in the glycerin solution of 50%, stops 1s, and then enters in 50 DEG C of aqueous solution, stop 20s, after cooling curing, obtain polypropylene hollow fiber separation membrane.
(3) hollow-fibre membrane is through up-coiler rolling, then hollow-fibre membrane is put into ethanol extracts, and extraction time is 36 hours;
(4) film extracted is taken out, drying obtains polypropylene hollow fiber separation membrane of the present invention after removing extractant, test its pure water flux and performance, INSTRON 3343 Material Testing Machine is adopted to test its hot strength 3.3MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 61%, and average pore size is 0.32 μm.Testing its pure water flux under 0.1MPa is 1276L/m
2h.
Embodiment 4
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 35%, melt index is 7g/10min, with the mixture of soya-bean oil and o-phthalic acid dibutyl ester for diluent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, and the mass fraction of diluent is 65%, be heated to 185 DEG C, and stir 1 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 1 hour, obtain casting solution;
(2) casting solution after filtration, and adopt measuring pump (parameter) that casting solution is delivered to spinning head, be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 165 DEG C; Extrude doughnut, first through the air gap of 6cm, then enter that temperature is 0 DEG C, mass fraction is in the glyceryl triacetate aqueous solution of 50%, stop 1s, and then to enter temperature be 25 DEG C, mass fraction is stop 10s in 50% glycerine, obtains polypropylene hollow fiber separation membrane after cooling curing.
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then hollow-fibre membrane is put into n-hexane extracts, and extraction time is 6 hours;
(4) film extracted is taken out, drying obtains polypropylene hollow fiber separation membrane of the present invention after removing extractant, test its pure water flux and performance, INSTRON 3343 Material Testing Machine is adopted to test its hot strength 4.9MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 58%, and average pore size is 0.23 μm.Testing its pure water flux under 0.1MPa is 1254L/m
2h.
Embodiment 5
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 30%, melt index is 3.1g/10min, with the mixture of corn oil and o-phthalic acid dibutyl ester for diluent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, and the mass fraction of diluent is 70%, be heated to 190 DEG C, and stir 2 hours under logical condition of nitrogen gas, stop stirring rear constant temperature standing and defoaming 2 hours, obtain casting solution;
(2) casting solution (temperature 190 DEG C) after filtration, and (casting solution is delivered to spinning head, and be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 160 DEG C to adopt gear-type metering pump; Extrude doughnut, first through the air gap of 8cm, then enter in the corn oil (mass percent 100%) of 40 DEG C, stop 2s, and then enter 20 DEG C, mass fraction is stop 20s in the sodium sulfate of polyethenoxy ether of fatty alcohol aqueous solution of 5%, obtains polypropylene hollow fiber separation membrane after cooling curing.
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then hollow-fibre membrane is put into methyl alcohol and n-hexane extracts 6h successively;
(4) film extracted is taken out, drying obtains polypropylene hollow fiber separation membrane of the present invention after removing extractant, test its pure water flux and performance, INSTRON 3343 Material Testing Machine is adopted to test its hot strength 4.5MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 50%, and average pore size is 0.12 μm.Testing its pure water flux under 0.1MPa is 1290L/m
2h.
Embodiment 6
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 30%, melt index is 3.1g/10min, take dibutyl phthalate as diluent, the mass fraction of diluent is 70%, is heated to 180 DEG C, and stirs 1 hour under logical condition of nitrogen gas, stop stirring rear constant temperature standing and defoaming 1 hour, obtain casting solution;
(2) casting solution (temperature) (filter parameter after filtration, filter criteria), adopt measuring pump (parameter) that casting solution is delivered to spinning head, be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 175 DEG C; Extrude doughnut, first through the air gap of 10cm, then enter in the Macrogol 200 (mass percent 100%) of 40 DEG C, stop 20s, and then enter soya-bean oil (mass percent 100%) the middle stop 5s of 0 DEG C, obtain polypropylene hollow fiber separation membrane after cooling curing.
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then hollow-fibre membrane is put into successively ethanol and extract 12h, extracts 12h in cyclohexane;
(4) film extracted is taken out, drying obtains polypropylene hollow fiber separation membrane of the present invention after removing extractant, test its pure water flux and performance, INSTRON 3343 Material Testing Machine is adopted to test its hot strength 4.1MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 52%, and average pore size is 0.20 μm.Testing its pure water flux under 0.1MPa is 1230L/m
2h.
Embodiment 7
A kind of preparation method of polypropylene hollow fiber separation membrane of improvement, concrete steps are with embodiment 2, wherein one-level coagulating bath is as follows: 20 DEG C, mass fraction be 10% dioctyl phthalate and mass fraction be stop 5s in the soya-bean oil of 90%, then enter 20 DEG C, be that the ethanol water of 90% stops 10s containing mass fraction, after cooling curing, obtain polypropylene hollow fiber separation membrane.
Test its pure water flux and performance, adopt INSTRON 3343 Material Testing Machine to test its hot strength 6.4.1MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 55%, and average pore size is 0.21 μm.Testing its pure water flux under 0.1MPa is 1485L/m
2h.
Comparative example 1
A preparation method for the polypropylene hollow fiber separation membrane of improvement, concrete steps are as follows:
(1) in the spinning still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 25%, melt index is 2.7g/10min, take soya-bean oil as diluent, the mass fraction of diluent is 75%, is heated to 200 DEG C, and stirs 0.5 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 0.5 hour, obtain casting solution;
(2) casting solution after filtration, and adopt measuring pump that casting solution is delivered to spinning head, be incorporated in spinning head using nitrogen as inner core liquid and form doughnut, spinneret temperature is 175 DEG C; Extrude doughnut, first through the air gap of 1cm, then enter in the water of 20 DEG C and stop 10s, after cooling curing, obtain polypropylene hollow fiber separation membrane.
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then hollow-fibre membrane is put into acetone, and extraction time is 3 hours;
(4) take out the film extracted, drying obtains polypropylene hollow fiber separation membrane of the present invention after removing extractant.Test its pure water flux and performance, adopt INSTRON 3343 Material Testing Machine to test its hot strength 6.4MPa, adopting PoreMaster 33 mercury injection apparatus to test its porosity is 43%, and average pore size is 0.51 μm.Testing its pure water flux under 0.1MPa is 15L/m
2h.
Claims (5)
1. a preparation method for the polypropylene hollow fiber separation membrane improved, comprises following steps:
(1) in the still of agitating device, polypropylene and diluent is added, polyacrylic mass fraction is 25 ~ 40%, polyacrylic melt index is 2.7 ~ 8g/10min, the mass fraction of diluent is 60 ~ 75%, be heated to 175 ~ 200 DEG C, under logical condition of nitrogen gas, stirring 0.5 ~ 3h, obtaining casting solution through adding thermal agitation, stop stirring rear constant temperature standing and defoaming 0.5 ~ 2h;
(2) after casting solution is filtered, and inner core liquid is incorporated in spinning head, spinneret temperature is 140 ~ 175 DEG C, extrude through spinning head together with casting solution, at first through air atmosphere, then enter secondary coagulating bath, be specially first through first order coagulating bath, again through second level coagulating bath, casting solution, through secondary coagulating bath cooling down, obtains polypropylene hollow fiber separation membrane after solidification;
First order coagulation bath temperature controls at 0 ~ 40 DEG C, and second level coagulation bath temperature controls at 0 ~ 80 DEG C;
First order coagulating bath constituent species select vegetable oil, phthalic acid ester, glyceryl triacetate, low-molecular-weight polyethylene glycol, glycerine, in triethylene-glycol any one or multiple, second level coagulating bath constituent species select in vegetable oil, water, ethanol, surfactant, glycerine any one or multiple;
In first order coagulating bath, the mass fraction of component is 10 ~ 100%; In the coagulating bath of the second level, the mass fraction of component is 5 ~ 100%;
(3) polypropylene hollow fiber separation membrane is through up-coiler rolling, then puts into one or more extractants and extracts, extraction time 3 ~ 48h;
(4) film extracted takes out after drying removes extractant and obtains polypropylene hollow fiber separation membrane.
2. the preparation method of the polypropylene hollow fiber separation membrane of a kind of improvement according to claim 1, it is characterized in that in step (1), polyacrylic mass fraction is 27 ~ 35%, polyacrylic melt index is 3 ~ 7g/10min, and the mass fraction of diluent is 65 ~ 73%.
3. the preparation method of the polypropylene hollow fiber separation membrane of a kind of improvement according to claim 1, it is characterized in that first order coagulation bath temperature controls at 0 ~ 20 DEG C, second level coagulation bath temperature controls at 20 ~ 50 DEG C.
4. the preparation method of the polypropylene hollow fiber separation membrane of a kind of improvement according to claim 1, is characterized in that the mass fraction of component in first order coagulating bath is 50% ~ 100%.
5. the preparation method of the polypropylene hollow fiber separation membrane of a kind of improvement according to claim 1, it is characterized in that the time of staying in first order coagulating bath is 1 ~ 20s, the time of staying in the coagulating bath of the second level is 1 ~ 20s.
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| CN104248916B (en) * | 2013-06-28 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of polypropylene separation membrane and preparation method thereof |
| CN104707490A (en) * | 2015-02-09 | 2015-06-17 | 杭州费尔过滤技术有限公司 | Method for preparing superfine polyolefin degassing membrane |
| CN110871037A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Hollow fiber separation membrane and preparation method thereof |
| CN112410909B (en) * | 2019-08-22 | 2023-04-07 | 中国石油化工股份有限公司 | Preparation method and application of porous fiber |
| CN112410911A (en) * | 2019-08-22 | 2021-02-26 | 中国石油化工股份有限公司 | Preparation method and application of coalescent fiber |
| CN112442750B (en) * | 2019-08-27 | 2023-05-09 | 中国石油化工股份有限公司 | Preparation method and application of fiber material for oil-water separation |
| CN112442749B (en) * | 2019-08-27 | 2023-04-11 | 中国石油化工股份有限公司 | Preparation method and application of fiber material |
| CN112442751B (en) * | 2019-08-27 | 2023-04-11 | 中国石油化工股份有限公司 | Preparation method and application of coalescent fiber for oil-water separation |
| CN112442752B (en) * | 2019-08-27 | 2023-05-12 | 中国石油化工股份有限公司 | Preparation method and application of polypropylene fiber for oil-water separation |
| CN112403289B (en) * | 2020-10-21 | 2021-09-07 | 清华大学 | Poly (4-methyl-1-pentene) hollow fiber membrane with gradient pore structure and preparation method thereof |
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| 《制膜条件对聚丙烯中空纤维微孔膜强度的影响研究》;李凭力等;《膜科学与技术》;20060831;第26卷(第4期);第20-23页 * |
| 凝固浴条件对聚醚砜膜结构与渗透性能的影响;李振雷等;《天津工业大学学报》;20080831;第27卷(第4期);第12-15页 * |
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